Cationic unsaturated amine-functional silane coupling agents

ABSTRACT

ORGANOSILICON COMPOUNDS OF THE FORMULA   *SI-Q-N(+)(-R&#39;&#39;)M-Z-C(-R&#34;)=CH2 Y(-)   IN WHICH Q I A DIVALENT HYDROCARBON RADICAL OR A DIVALENT HYDROCARBON RADICAL CONTAINING OXYGEN IN THE FORM OF -COC-,   -COO-C-, -CO-, OR -C-OH   GROUPS OR NITROGEN IN THE FORM OF   -N(-R&#34;)-   GROUPS; Z IS A DIVALENT ORGANIC RADICAL HAVING A DOUBLE BOND CONJUGATED WITH THE   -C(-R&#34;)=CH2   MOIETY, Z BEING BONDED TO THE NITROGEN ATOM BY A C-N BOND; R&#39;&#39; IS INDEPENDENTLY SELECTED FROM THE GROUP CONSISTING OF THE HYDROGEN ATOM, LOWER ALKYL RADICAL OR A HEATROCYCLIC ORGANIC COMPOUND CONTAINING THE NITROGEN ATOM AS A RING MEMBER; M IS AN INTEGER OF 1 TO 2; R&#39;&#39;&#39;&#39; IS THE HYDROGEN ATOM OR A LOWER ALKYL RADICAL, AND Y IS AN ACID ANION; ARE DISCLOSED. THE COMPOUNDS, FOR EXAMPLE   1-((C3H7-O-)3-SI-CH2-CH2-),4-(CH2=CH-C(-CH3)=CH-CH2-   N(+)(-CH3)2-)BENZENE BR(-)   AS COUPLING AGENTS FOR PROMOTING THE ADHESION OF ORGANIC POLYMERS TO SOLID INORGANIC SURFACES.

United States Patent 3,819,675 CATIONIC UNSATURATED AMlNE-FUNCTIONAL SILANE COUPLING AGENTS Edwin P. Plueddemann, Midland, Mich., assignor to Dow Corning Corporation, Midland, Mich.

No Drawing. Application Dec. 17, 1970, Ser. No. 99,228,

which is a continuation-in-part of abandoned application Ser. No. 825,035, May 15, 1969. Divided and this application Jan. 15, 1973, Ser. No. 323,595

Int. Cl. C07f 7/10, 7/18 US. Cl. 260-448.8 R Claims ABSTRACT OF THE DISCLOSURE Organosilicon compounds of the formula 69 9 ESi-Q,NZC=CH2 Y Di II in which Q is a divalent hydrocarbon radical or a divalent hydrocarbon radical containing oxygen in the form of COC-,

groups or nitrogen in the form of RHb I groups;

Z is a divalent organic radical having a double bond conjugated with the moiety, Z being bonded to the nitrogen atom by a CN bond;

R is independently selected from the group consisting of the hydrogen atom, lower alkyl radical or a heterocyclic organic compound containing the nitrogen atom as a ring member;

m is an integer of 1 or 2;

R" is the hydrogen atom or a lower alkyl radical; and

Y is an acid anion; are disclosed.

The compounds, for example as coupling agents for promoting the adhesion of organic polymers to solid inorganic surfaces.

This is a division of application Ser. No. 99,228, filed Dec. 17, 1970; which in turn is a continuation-in-part of application Ser. No. 825,035; filed May 15, 1969; now abandoned.

Organosilicon compounds having amino substituents have attained considerable commercial success as coupling agents to improve the adhesion of certain polymeric materials to siliceous substrates. Aminopropylsubstituted silanes and aminoethylaminopropyl-substituted silanes are representative of the Organosilicon compounds utilized in such bonding applications in conjunction with phenolic and melamine type resins. Ethylenically unsaturated silanes, such as vinyltrichlorosilane, are used in these applications when bonding with vinylic polymers. To date, the amine-functional silanes have not been used as the sole component of coupling agents for vinylic polymers.

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It has been found that the compositions claimed herein provide excellent adhesion of organic polymers to siliceous surfaces, for example, when the unsaturated amine-functional silanes of the invention are applied in their cationic form to siliceous reinforcing surfaces the adhesion of vinylic polymers to the surface is greatly improved. The compositions of the invention can also be used as a sizing on glass fibers to minimize the build-up of static charge on the fibers.

Thus, it is an object of the invention to provide novel cationic Organosilicon compounds which have utility as coupling agents.

It is another object of the invention to provide high strength articles made from vinylic polymers and siliceous reinforcing materials.

The compositions of the invention have the general formula R3 n Rim RI! and partial condensates thereof, in which X is the hydroxyl group or a hydrolyzable radical;

R is a lower alkyl radical;

Q is a divalent hydrocarbon radical or a divalent hydrocarbon radical containing oxygen in the form of -COC-,

groups or nitrogen in the form of R is independently selected from the group consisting of the hydrogen atom, a lower alkyl radical or a heterocyclic organic compound containing the nitrogen atom as a ring member;

m is an integer of 1 or 2;

Z is a divalent organic radical having a double bond conjugated with the moiety, Z being bonded to the nitrogen atom by a C-N bond;

R" is the hydrogen atom or a lower alkyl radical;

n is an integer having a value of from 1 to 3 inclusive;

and

Y is an acid anion.

As described above, X is the hydroxyl group or a hydrolyzable radical, such as alkoxy radicals, for example, methoxy, ethoxy, isopropoxy, butoxy and isobutoxy; aryloxy radicals, for example, phenoxy; halogen atoms, for example, chlorine, bromine and fluorine; acyloxy radicals, for example, acetoxy, propionoxy and decanoxy; ketoxime radicals, for example,

and amine radicals for example, CH NH-, NH, and (C H N. As used herein hydrolyzable group is taken to mean any radical which will react with water at room temperature to form a silanol.

R is a lower alkyl radical containing no more than 6 carbon atoms, for example, methyl, ethyl, isopropyl, butyl or a hexyl radical. The same or different IR substituents can be attached to the same silicon atom.

For purposes of this invention, the linking group, Q, between the silicon atom and the nitrogen atom, is composed of carbon, hydrogen and oxygen, the latter being in the form of carbonyl, ether, ester and hydroxyl groups or nitrogen in the form of an amine group. Specific examples of Q are divalent hydrocarbon radicals such as the propylene radical, the (-CH radical, the (CH radical and (CH radical and branched chain radicals such as --CH: CHr-fi carbonyl groups such as ether radicals such as CH CH CH OCH CH CH and --CH CH CH (OCH CH OCH CH; ester groups such as (in, CH; c1130 0 0 (JHC o 0 CH,); and CH1CH;CH;O 2 Ji3HCH1; or groups containing hydroxyls such as OH 0H,GH,CH, JHCH GH;

or a combination of such groups as OH CH:CH2CH1 O CHfl IHCHP.

Also, Q can contain nitrogen, for example --CH CH CH NI-ICH CH d NCH in i v. 2H5 H3 R is independently selected from the group consisting of the hydrogen atom, a lower alkyl radical such as described with respect to R or heterocyclic organic compound containing the nitrogen atom as a ring member, for example,

HO OH and I N 014, GH, C2\$HI HG CH H2 H, CH: 0111' Hii---iiH Of course when R is such a heterocyclic compound, m is equal to 1, whereas when R is a hydrogen or lower alkyl radical, m is equal to 2.

Z is a divalent organic radical composed of carbon, hydrogen and oxygen such as described with respect to the Q radical, further characterized as having a double bond conjugated with the vinylic moiety. Z is bonded to the nitrogen by a carbon-nitrogen bond. Illustrative of such divalent radicals are arylene radicals, such as the phenylene, biphenylene,

radicals; carbonyl radicals, for example Hii--CH:

and vinylic groups, such as R" is the hydrogen atom or a lower alkyl radical such as described with respect to R.

Y is a halogen atom; chlorine, bromine, or iodine; or other acid anion, such as carboxylate anions; for

4 example, formate and acetate anions; the phosphate anion, the sulfate anion; the nitrate anion and the like.

Thus the following are illustrative of compounds within the scope of the invention:

6B 9 (CgHgOhSiCHz CH CH2O CHzNHCHgCHzC-CH=CH1 Cl 9 -CH=CH: CH;G O 0, and

Partial condensates of the cationic unsaturated aminefunctional silanes are also within the scope of the invention. Partial condensate" is meant to imply that a detectable amount of the hydroxyl or hydrolyzable groups remain uncondensed in the compositions, preferably at least one such group per every four silicon atoms remains uncondensed. The partial condensate is a polymer of -SiOSiO- units with the silicon atoms retaining their cationic functionality and the requisite amount of hydroxyl groups, the hydroxyl or hydrolyzable groups being available to form bonds with inorganic substrates when the polymer is used as a coupling agent or primer.

The compounds of the invention can be prepared by reaction of a conjugated unsaturated alkylhalide with an aminofunctional silane. This reaction is carried out in a suitable solvent, with conditions of time and temperature varying widely. A second method of preparation, analogous to the first, is the reaction of silyl-substituted alkylhalide with a conjugated unsaturated aliphatic amine to produce the cationic compounds. Both of these reactions are carried out in a suitable solvent, such as dimethylformamide, l-methoxy-Z-propanol, I-Z-dimethoxyethane, tertbutyl alcohol, isopropanol, methanol and diacetone alcohol. Certain of the cationic compounds are obtained by dissolving the neutral unsaturated secondary and tertiary amine in an acid solution, such as dilute sulfuric acid. These methods of producing the compounds are illustrated in detail in the examples.

The cationic unsaturated amine-functional silanes are soluble in aqueous media to the extent that at least 5 weight percent solutions are readily formed. These solutions can be applied to solid inorganic materials by conventional techniques such as dipping, brushing or spraying. The solid inorganic material treated in this manner then has attached to its surfaces the hydrolyzate of the formula I R. l

in which all radicals are as previously defined.

This hydrolyzate may be in the form of a partial condensate in which a dectectable amount of hydroxyl or hydrolyzable groups (preferably at least one such group per every four silicon atoms) remain uncondensed and are then available for reaction with sites on the inorganic surface to provide chemical bonding. Although not wishing to be bound by theory, it is believed that the ESlOH radicals in the coupling agent react with silicon-bonded hydroxyl groups on siliceous surfaces or with metal oxides on metal surfaces to form the chemical bond. Contrary to thistheory, and thus unexpectedly, certain amine hydrochlorides of the invention provide increased adhesion between vinylic polymers, such as acrylates and gold, a metal which is not subject to oxidation.

Cationic treated siliceous materials can be combined with organic resins, such as polyester-styrene resins, to provide reinforced articles. Superior strength is imparted to these articles because the interface of the resin and the siliceous material is formed by reaction of the organic polymer and cationic compound in one instance and the reaction of ESiX groups and water on the solid in the other instance. It is believed that the enhanced properties of such a composite are, at least in part, provided by an ordering or alignment of molecules at the interface which is a result of their cationic nature.

Organic polymers include thermoplastic and thermosetting polymeric materials, both of the condensation type, such as the polyamides and the vinylic type, such as the polyolefins. Representative of condensation polymers are the acetal polymers, such as made by the copolymerizetion of propylene oxide and formaldehyde; alkyd resins, such as are synthesized by reacting a saturated polybasic acid with a polyol; amino resins, such as the reaction products of urea or melamine with formaldehyde; epoxy resins, such as those derived from bisphenol A and epichlorohydrin; phenolic resins, both resols and novolaks; polyamides, such as the reaction product of hexamethylene diamine and adipic acid; polycarbonates, such as the reaction products of bisphenol A and a carbonate diester; polyester resins, such as poly(ethylene terephthalate), and polysulfone resins, such as those made by the reaction of the disodium salt of bisphenol A and 4,4'-dichlorodiphenylsulfone. The aliphatically unsaturated monomers suitable for polymerization and fabrication of the above-described reinforced composite include styrene, acrylonitrilebutadiene-styrene, acrylonitrile-styrene, isobutene, styrenebutadiene, ethylene, propylene, vinylacetal, vinylchloridevinylidene, methylmethacrylate, and ethylene-propylenecyclohexadiene. The polymers, formed by polymerization of the aliphatically unsaturated carbon-carbon bonds, can be rigid materials, such as polyester resins or elastomeric materials, such as styrene-butadiene rubber, and as a class are conveniently designated as vinylic polymers. When vinylic polymers are used in combination with unsaturated amines of the invention, especially the amine hydrochlorides, it may be desirable to add a free radical initiator to promote reaction between the polymer and the unsaturation of the amine. The free radical source should be one which is active at the bonding temperature, thus, dicumyl peroxide is preferred for use with polypropylene, and benzoyl peroxide is preferred for use with styrene-containing polymers.

Solid siliceous materials commonly used for reinforcing organic polymers include glass, in the form of cloth,

strands and chopped fibers; silica, asbestos, mica, talc, and quartz. An additional advantage is realized when fibrous materials are treated since the cationic compounds minimize the build-up of static charge in the fibers and thereby facilitate the handling of strands, rovings and the like.

As an alternative to treating the solid reinforcing material and then forming the composite, the cationic compounds of the invention can be copolymerized with the unsaturated monomers, such as methylmethacrylate, styrene and vinyl acetate, to form a vinylic polymer which in turn can be combined with untreated reinforcing material to form the composite. Generally the copolymers of the invention contain from 0.5 to 5 mol percent of the cationic amine-functional units. The copolymers are produced by vinylic polymerization with conventional catalysts by emulsion polymerization, solution polymerization and other methods which are Well known for polymerization of the particular monomer. Of course, the vinylic polymers must be in such a physical state (i.e.; softened or melted) that the untreated reinforcing material can be incorporated therein or laminated thereto.

Also, within the scope of the invention is the formation of the cationic coupling agents in situ during production of composite articles. This can be accomplished by coating the substrate or reinforcing material with one reactant necessary to the formation of the cationic compound and coating the solid vinylic polymer with the other reactant. For example, when polyethylene film is dipped in a solution of vinylbenzyl chloride and then pressed at temperatures of about 200 C. onto aluminum panels primed with n-beta-(aminoethyl)gammaamino-propyltrirnethoxysilane, a strong bond between the aluminum and polyethylene is obtained.

In addition to their utility as coupling agents on siliceous reinforcing materials, the cationic compositions of the invention are primers for bonding other inorganic solids, for example metals, such as aluminum, magnesium, zinc, tin, chromium, titanium or steel to the organic polymers. The alkaline minerals are another class of in organic solids useful in the formation of composite articles. Polyester castings utilizing an amine hydrochloride coupling agent and filled with granular calcium phosphate show much greater flexural strength than the same type of casting in which the coupling agent was omitted. Calcium phosphate is one of the principal components of tooth enamel, thus the amine hydrochlorides have utility as adhesive aids in dental restorations.

The amine hydrochlorides of the invention (wherein at least one R radical is a hydrogen atom) are especially useful as primers for increasing the adhesion of vinylic polymers to gold. This is unexpected since gold does not oxidize, and it is generally thought that an oxidized or bydroxylated surface is necessary to obtain good bonding. Good adhesion of vinylic polymers, such as the acrylic resins, to gold surfaces is of special importance in the fabrication of dental restorative prosthetic devices.

The copolymeric cationic materials of the invention also exhibit the increase in bond strength. For example, when copolymerized with acrylic esters, the cationic acrylate forms a thin hard film, which when cured, adheres tenaciously to common structural material, such as steel or ceramic surfaces. The copolymers can be pigmented and used as paint compositions.

The following examples are illustrative of the invention, which is properly delineated in the appended claims.

EXAMPLE 1 A mixture of 50 grams of 3-chloropropyltrimethoxysilane (0.25 mol), 0.5 grams of methyliodide, 50 grams of 2-(dimethylamino)ethyl methacrylate (0.32 mol), 100 grams of dimethylformamide and 0.5 grams of sulfur was maintained at C. for 24 hours, after which time titration showed 0.21 equivalents of halide ion present. After a total of 50 hours heating at 95 C., titration showed 9 parts styrene monomer, to which was added 0.5 parts benzoyl peroxide dissolved in about 7.5 parts styrene monomer. The linear polyester in the resin mixture was prepared from phthalic acid and maleic acid in equimolar proportions reacted with polypropylene glycol, the 70 per- 10 compositions 2 and 3, are elfective but to a limited extent when compared with the compositions where n is 3.

EXAMPLE 3 A mixture of 18.7 grams (0.1 mol) of cent solution of this polyester 1n styrene having an acid number of about 35. (CH3O)3S1CH2CH2CHZN(CH3)2 The flexural strengths of the laminates were determined 9 grams of methacrylic acid, grams of epichlorohydrin maccordance with U.S. Federal Speclfication 406b in 40 grams of t-butyl alcohol and 0.1 grams of sulfur Method 1031. Flexural strength was also determmed on 10 (as stabilizer) was refluxed for 3 hours. Titration indicated samples of the laminates WhlCh had been immersed 1n the presence of 0.1 mol equivalent of chloride ion. The boiling water for 2 hours and then wiped dry, this being product was a test which is recognized as roughly the equivalent of OH CH, standing in water at room temperature for one month. 69 I e The results of the latter test will be referred to hereafter (amokslcHtCmCHzNCHtCHCHtOC' as the 2 Hour Boil data. The 2 hour boil flexural (CH3); strength multiplied by 100 and divided the strength of the laminate as molded is reported as the Percent Retention Ten milliliters of the reaction mixture was mixed with of laminate strength. The following results were obtained 250 milliliters of 1,2-dimethoxyethane to precipitate a on the above prepared laminates. granular solid. This solid was separated by filtration and TABLE II Laminate properties Flexural strength,

p.s.l.

Compo- Percent sltlon Formula of coupling agent on glass cloth Dry 2 hr. boil retention 1 (CHaO);SiCHzOHzCHzNWHahCHzCHzOC0O(CH )=CH 01 90,300 79,200 88 2 (CH)2S1(CH3)CH2N(CH3)ZCH2CH2OCOC(CH3)CH2 01 51,500 18,500 30 a CHgOS1(CH3)2CH2N(CH )2CH2CH2OC0C(CH )=CH c1 59, 400 32,400

4 (CIIaOhSi-CH N CH92CHCH OCOC(CH )=CH 01 86,300 80,000 03 5 Same as above... Br 78,600 75,900 96 G (CH O)3SiCH2CHzCH N(CH3)2CHzCH20C0C(CH )=CH I 75,900 75,000 98 7 (omonsionm 01192011201320oo0(0H3 =0H5 01 84, 000 79,000 94 s (C11 0):SiCHzCHz@CH N(CHmCHZCH OCOC(CH )=CH c1 71, 200 71,300 100 9 (CHaOhS1CHzCHzCH2N(CHa)2CHgCHzOCOC(CH )=CH2 CI 10 (C1130);SlCH2CH2CH2N(CHQ)2CH2@CH=CH 01 86,300 80,000 93 11 0H,o 3s1@-oH2NH to4H, (3112011200oc 0H, =oH, Bl' 79,000 04, 200 81 12' (CH OhSiCHzCHzCHzNEHCHg)CH; -CH=CH 01 91,200 86,700 05 13 (CQH O);SiCHzCHgCHgNHzCHz CH=0H, 01 89,000 78,100 89 14' (CH OhSi(CH2)aNCHzCHzNHzCHz-@CH=CH1 c1 B7, 000 80,700 93 15 omopsioHzcEuomN(CH; 0H20H=CH2 01 23,400 10,200 43 10 (CHaO);SiCHzCHaGHzN(CH3)2CH2CH2O CH=CHI 01 as, 100 18,500 50 Control... No coupling agent on glass. 38, 700 12, 300 32 Treated glass was rinsed in dilute aqueous ammonia solution.

con are preferred Compositions where n is 1 or 2, as in 75 dried to recover 5 grams of the pure product. The solid was soluble in water and titrated for an 9 9 Equivalent weight of 370/ C1; theory=865/ 01.

Glass cloth, treated with an 0.1% aqueous solution of the above product was laminated with polyester resin and tested for flexural strength in the same manner as described in Example 2. Results are tabulated below:

Flexural strength p.s.i. 75,400

2 hour boil p.s.i. 63,300

Percent retention percent 84 EXAMPLE 4 A mixture of 14 grams (0.1 mol) of glycidyl methacrylate and 17 grams (0.1 mol) of (CH O) SiCH CH CH NI-ICH was allowed to stand at room temperature. After 24 hours the product was a clear viscous oil which did not contain any epoxy or free secondary amine. Gas-liquid chromatography indicated that there was no unreacted starting material in the product. Infra-red spectroscopy identified the methacrylate double bond and was consistent with the following proposed structure:

A second nonionic agent was prepared by allowing a mixture of and 1'3 butylene dimethacrylate to react at room temperature. After 2 days the material had reacted to form the two isomers:

In addition, the reaction mixture contained an equivalent amount of the bis-adduct and a small amount of unreacted butylene dimethacrylate.

A third nonionic agent was prepared by reacting a mixture of 25 grams of and 18 grams of CH =C(CH )COOCH CH NH(t-butyl) with 1 gram tris(dimethylaminoethyl) phenol catalyst and 0.2 grams of sulfur stabilizer at 100 C. for 8 hours. The amber oily product contained only a trace of starting materials and retained the methacrylate double bond as identified by its infra-red spectrum. The product was insoluble in water, but soluble in 50% aqueous acetone or dilute aqueous hydrochloric acid.

A portion of the above products were converted to their cationic form by addition of dilute aqueous hydrochloric acid. The remaining portions of the products were added to dilute aqueous acetone solutions to form a non-ionic treating formulation. Glass microscope slides were treated by soaking for 15 minutes in the hydrochloric or acetone solutions and drying for 30 minutes at room temperature. The polyester resin described in Example 2 was applied to the glass slides and cured for one hour at 100 C. Adhesion of the cured polyester to the treated slides was tested qualitatively by attempting removal of the resin with a razor blade after initial cure and after 3 days immersion in water.

The cationic form (chlorides) proved to be very good coupling agents-the resin adhering strongly to the glass, even after 3 days in waterwhile the nonionic form of the products (applied from acetone) gave only limited increase in adhesion which was lost after immersion in water.

EXAMPLE The importance of the cationic nature of the compounds of the invention is illustrated by the following: The compound,

prepared as described in Example 4, was applied to glass cloth from isopropanol-water, dilute aqueous acetic acid and dilute aqueous hydrochloric acid. The cloth was laminated with polyester resin and tested as previously described. The cationic nature of the amine increases in the order given below:

Laminate properties Flcxural strength Solution of amine-functional silane Percent coupling agent Dry 2 hr. boil retention 0.1% isopropanol-water. 30, 000 54 0.5% isopropanol-water. 49, 500 67 0.1% dilute acetic acid 63, 600 88 0.1% dilute hydrochloric acid-.. .400 62, 500 78 It can be seen that the cationic agents were superior to the same compound applied from the non-ionic isopropanol-water solution. A five-fold increase of coupling agent in the isopropanol-water solution did not give improvement equivalent to the weaker of the two cationic forms, the acetate salt. Comparison of wet strength retention of the laminates also demonstrates the superiority of the cationic form.

EXAMPLE 6 When 2-3 mole percent of G9 6 {(CH OhSiCHzCH CH N-CH CHzO-C-CH=CH cmcoo 3): is copolymerized with butadiene to form an elastomer and the copolymeric rubber is then bonded to untreated glass tire cord fabric by techniques conventional in the rubber industry, there is obtained a reinforced rubber article of enhanced strength.

EXAMPLE 7 When 1-5 mol percent of 0 cm 9 it a. (C4H00)3S1CH;CH3CH1NCH1CH1O =CH C1 is copolymerized with -99 mol percent of a mixture of ethylacrylate, methylmethacrylate as a 40% solution in cellosolve acetate, there is obtained a clear acrylic copolymer, which when filmed on metal surfaces and baked at C. is converted to a clear, hard coating with improved adhesion and solvent resistance.

EXAMPLE 8 (CH O) Si(CH OOCC(CH =CH Results are as follows:

Coupling agent Log r (CHah O CHa 8. 01 (C1130):Sl(CHz7)3$CHgCHgOC-C=CH,

13 The lower log value obtained by use of the cationic composition signifies the better charge dissipation which facilitates handling of the glass fibers.

EXAMPLE 9 Composite articles of wollastonite filled polypropylene were prepared by injection molding'The molding composition was prepared by mixing 100 parts by weight of wollastonite with 0.5 weight percent of an amine hydrochloride coupling agent (Composition No. 14 of Example '1) in a Waring Blendor for one minute.,The wollastonite was then mixed with 150 parts by weight of commercially available powdered polypropylene. In certain. instances, weight percent of a vinylic monomer and one weight percent of dicumyl peroxide (catalyst) were added to form in situ a cationic amine functional copoly-v mer as the coupling agent. The injection molding apparatus was operated on a 45 second cycle at an injection pressure of 600 p.s.i. at the following temperatures: rear heater, 430 F.; frontheater, 470 F.; and mold, 120 F. Flex and tensile bars were molded and tested. The table relates the coupling agents used to the test results. The recorded data are the average of five test results.

Strength Flexural modulus (p.s.i.)

i Flexural (p.s.i.)

Tensile (p.s.i.)

Coupling agent These data demonstrate the superior strengths obtained by use of the cationic amine functional coupling agents of the invention.

EXAMPLE 10 Clean aluminum panels were wiped with a 10 percent solution of the reaction product of beta-aminoethyl-gammaaminopropyltriethoxysilane and vinylbenzyl chloride in 2-methoxyethanol. The primed panels were air dried for five minutes and then pressed against molten polymers of various chemical structure. The bonding conditions for the diiferent polymers are noted below. All of the polymers are commercially available materials. After cooling to room temperature, adhesion was determined qualitatively by loosening a portion of the polymeric film with a razor blade and pulling. Adhesion was considered nil when the film detached from the panel without pulling and excellent when there was cohesive failure or the film could not be pulled from the panel. Adhesion of the different polymeric films 1s listed below.

TABLE III Bonding conditions Tempera- Polymer ture, C. Time Adhesion Polypropylene- 200 10sec. 0.1 High density polyethylene. 200 1 see- C.F. Polystyrene 200 1 min. 0.1 Polyamlde. 300 15 sec. O.F. Polycarbonate 250 30 sec-.- C.F. Polyvinyl acetate. 175 1 min- 0.1. Cellulose acetate 225 10 sec. Good. Polyvinyl chloride- 200 1 min- C.F. Poly(styrene-acrylonit 225 1 min..- Good. Poly(acrylonitrile-butadiene styrene)- 225 1 mm C.F. Styrene-butadiene elastomer 225 1 mm--- Very good. Polyionnal 250 1 min... C.F. Saturated polyester (Mylar). 250 1 min. OF. Polysulione- 275 1 min- Fair. Polyvinylidene chloride 200 311mm... C.F. Poly(chlorotrifiuoroethylene) 300 1 min. Good.

Nora-0.1. indicates cohesive failure.

These data demonstrate that the coupling agents of the invention are effective with a wide variety of polymers including condensation polymers, such as polycarbonate, and vinylic polymers, such as polystyrene.

EXAMPLE 11 The coupling agent utilized in Example 10 was used to increase the adhesion of molten polyethylene in a variety of substrates. Each substrate Was primed with the coupling agent solution described in Example 10. High density polyethylene was then bonded to the primed surfaces by pressing lightly under the conditions indicated. For purposes of comparison, adhesion of polyethylene bonded under the same conditions to unprimed surfaces was also determined. Results are as follows:

TABLE IV Bonding conditions Temper- Adhesion ature Substrate C. Time Primed Unprimed Aluminum 200 3minutes. C.F Poor 2 o C.F Nil. 200 1minute C F Nil. 200 do C.F. Poor 200 3minutes. Good... Very poor. Chrome-plate steel--. 200 do do Fair. Cold-rolled steel 200 do Very good- Do. Tin-coated steel- 200 do G P Titanium 250 o 0-. Ceramic tile 200 .do Glazed clay til 200 1 minute. 0. Silver 200 do C.F Do. Gold 200 do Very good... Very poor.

N o'rE.-C.F. indicates cohesive failure.

EXAMPLE 12 Bonding in accordance with the present invention was accomplished by the in situ formation of amine hydrochlorides. Glass microscope slides were primed with a 10 percent solution of an amine-functional silane. The solvent was 2-methoxy-ethanol. Granules of a commercially available polypropylene (Profax 2303 from Hercules Incorporated, Wilmington, Del.) were primed with a 10:1 mixture of vinylbenzyl chloride and dicumylperoxide diluted to 10 percent reactive ingredients with 2-methoxyethanol. The treated granules were pressed onto the treated slides for one minute at 250 C., cooled to room temperature and examined for adhesion. For purposes of comparison, the adhesion of untreated polypropylene granules bonded to treated glass slides was also determined. Results are given below:

Adhesion to class Of untreated Of treated Silane on glass polymer polymer None Nil Nil. (CgH5O)3SiCH2CH OH2NH Very poor Good. (CHIlO)3Sl(CH2)3NHCH CH NH: do Cohesive failure.

These results show that the amine hydrochloride was formed in situ and did increase adhesion of the polymer to the glass.

EXAMPLE 13 Flex strength (p.s.i.) of castings filled with- 487 437 437 magne- COupling agent CaCOg Caa(PO4)i siurii silicate None 9, 970 4, 500 10, 600 Composition No. 14 of Example 2.- 11, 700 9, 290 12, 370

15 EXAMPLE 14 Adhesion promotion of vinylic polymers to gold was demonstrated by priming Type III, hard, 20 DWT dental gold with a solution of the same coupling agent used in Example 13 and coating the primed gold with an acrylic dental resin (Vinacryl from Cosmos Dental Products, Inc.). The acrylic resin paste was cured to 140 C. for 30 minutes. Adhesion of the cured acrylate to primed and unprimed gold was compared after cooling to room temperature and after soaking in water. The cured resin showed fairly good dry adhesion to the unprimed gold, being removed only with difliculty, but after soaking in water for eight hours the resin detached of its own accord from the gold. Adhesion of the cured resin to the primed gold was excellentthere was cohesive failure of the resin during attempts to remove it from the primed surface. After soaking in water for three days, attempts to remove the resin from the primed gold surface again resulted in cohesive failure in the resin.

That which is claimed is:

1. A composition of the formula GB 6 XnSiQ,NZ-C=CHz Y Rel n Rim RI! and partial condensates thereof, in which X is the hydroxyl group or a hydrolyzable radical;

R is a lower alkyl radical;

n is an integer having a value of from 1 to 3 inclusive;

Q is a divalent hydrocarbon radical or a divalent hydrocarbon radical containing oxygen in the form of --COC,

-o 00-, -oor 1:011

g l l groups or nitrogen in the form of are groups;

R is independently selected from the group consisting of the hydrogen atom, a lower alkyl radical or a heterocyclic organic compound containing the nitrogen atom as a ring member;

m is an integer of 1 or 2;

Z is an arylene radical having a double bond conjugated with the -o=orr,

moiety, Z being bonded to the nitrogen atom by a CN bond; R" is the hydrogen atom or a lower alkyl radical; and Y is an acid anion.

2. A composition in accordance with claim 1 where n is equal to 3.

3. A composition in accordance with claim 1 wherein m has a value of 2 and at least one R radical is a hydrogen atom.

4. A composition in accordance with claim 1 wherein Z is a radical.

5. A composition in accordance with claim 1 wherein Q is selected from the group consisting of the formula z, z)3-,

9. A composition in accordance with claim 7 of the formula 10. A composition in accordance with claim 7 of the formula References Cited UNITED STATES PATENTS 3,373,137 3/1968 Saam 260448.8 R X 3,580,920 5/1971 Culpepper 260448.8 R X 3,661,963 5/1972 Pepe et al. 260448.2 N

DANIEL E. WYMAN, Primary Examiner P. F. SHAVER, Assistant Examiner US. Cl. X.R.

117-124 F, 126 GN, 126 GQ; 260448.2 N 

